Influence of Multidirectional Interactions on Domain Size and Shape of 2-D Molecular Assemblies

The effect of molecule-molecule interactions on the size and shape of two-dimensional (2-D) ordering domains was investigated using scanning tunneling microscopy (STM) at the liquid/solid interface. Synthesized alkoxybenzene derivatives bearing amide group tend to form very large domains of 2-D orderings (>0.25 μm²), whereas the domain size of corresponding urea derivatives was significantly small in the same condition. The quantitative analysis of the concentration dependence of surface coverage using a nucleation-elongation model suggests that the replacement of amide functionality by urea increased the equilibrium constant of the nucleation process of 2-D self-assembly, which is a key factor for the domain size at the liquid/solid interface. Interestingly, the STM observation revealed that a slight difference of molecular structure influences the shape of 2-D ordering domains, and needle-shaped domains with large aspect ratio around 10 were observed by tuning molecule-molecule intramolecular interactions in 2-D self-assembly formed at a liquid/graphite interface.